Bifunctional reactive polyhedral oligomeric silsesquioxane (POSS) of 3, 13‐divinyl octyphenyl silsesquioxane (DV‐DDSQ) and 3, 13‐dihydro octyphenyl silsesquioxane (DH‐DDSQ) were used as additive to modify ethylene‐propylene‐diene rubber (EPDM), and double vinyl groups or active hydrogen groups of bifunctional reactive POSS (brPOSS) underwent a cross‐linking reaction with the active hydrogen groups and double bonds of EPDM, to investigate the effect of brPOSS regulating functional reaction group on the properties of EPDM. Crosslinking density, mechanical properties, thermal stability and ablation performance of brPOSS modified EPDM were investigated, and the pyrolysis behavior and surface structure of modified EPDM was analyzed by X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Furthermore, the ablation performance of brPOSS modified insulation based on EPDM was investigated. The results showed that the tensile strength of EPDM/DV‐DDSQ and EPDM/DH‐DDSQ increased by 35.8% and 55.3% respectively compared with EPDM; the tear strength increased by 6.4% and 5% than that of EPDM. Moreover, the 5% initial thermal decomposition temperature based on thermogravimetric analysis (TGA) and mass (or linear) ablation rate ablative performance of brPOSS modified EPDM were optimized to a certain extent, and the ablative performance of brPOSS modified insulation based on is significantly improved, the mass ablation rate of DV‐DDSQ/insulation and DH‐DDSQ/insulation decreased by 35.4% and 41.6% respectively, and linear ablation rate decreased by 38.2% and 39.4% respectively.
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